The present invention relates to novel fungicidal imidazolinone and imidazolinethione compounds for use in plant protection. It also relates to the processes for the preparation of said compounds and to the compounds which can optionally be used as intermediates in the preparation processes. It further relates to the use of these compounds as fungicides, to fungicidal compositions comprising these compounds and to methods for combating fungal diseases in crops using these compounds.
One object of the present invention is to provide compounds showing improved properties in the treatment of fungal diseases.
Another object of the present invention is to provide compounds showing a spectrum of use in the field of fungal diseases which is also improved.
In a first major aspect of the present invention, it has been found that these objects can be achieved by virtue of compounds of the invention which are 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives of the general formula (I): 
wherein:
W is a s or oxygen atom or an Sxe2x95x90O group;
A represents O or S;
n=0 or 1;
B represents NR5 or O or S or CR5R6 or SO2 or Cxe2x95x90O;
R1 and R2, which are identical or different represent:
H, provided that one of the two groups is different from H;
an alkyl or haloalkyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical having 2 to 6 carbon atoms;
a dialkylaminoalkyl or cycloalkyl radical having 3 to 7 carbon atoms;
an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7; or
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above;
or R1 and R2 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R7;
R3 represents:
an alkyl group having 1 to 6 carbon atoms;
an alkoxyalkyl alkyl1thioalkyl, alkysulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms;
a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamaoylalkyl group having 3 to 6 carbon atoms;
a N,N-dialkylcarbamoylalkyl group having 4 to 8 carbons atoms; or
an arylalkyl group, the alkyl part being a radical having 1 to 6 carbon atoms and the aryl part being phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted by 1 to 3 groups chosen from R7;
R4 represents:
a hydrogen atom (when n is equal to 1);
an alkyl group having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms;
a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms;
a N,N-dialkyl carbamoylalkyl group having 4 to 8 carbon atoms;
an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7;
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above;
an amino group disubstituted by two identical or different groups chosen from:
an alkyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkenyl or alkynyl radical having 3 to 6 carbon atoms;
a cycloalkyl radical having 3 to 7 carbon atoms;
an arylalkyl, such as defined above, phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7; and
a thienylmethyl or furfuryl radical; or
a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by aryl having 1 to 3 carbon atoms;
R5 represents:
H, except when R4 is H;
an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or cyanoalkylsulfonyl radical having 2 to 6 carbon atoms;
an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical having 3 to 6 carbon atoms;
a formyl radical;
a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical having 3 to 6 carbon atoms;
a cycloalkylcarbonyl radical having 4 to 8 carbon atoms;
a phenyl; arylalkylcarbonyl, especially phenylacetyl or phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups chosen from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups chosen from R7; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)carbonyl; (pyridylmethylthio)carbonyl; or arylsulfonyl radical;
a carbamoyl radical, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R7 groups;
a sulfamoyl group, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R7 groups; or
an alkylthioalkylsulfonyl group having 3 to 8 carbon atoms or a cycloalkylsulfonyl group having 3 to 7 carbon atoms;
R6 represents:
a hydrogen atom;
a cyano group;
an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms;
an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms; or
a benzoyl group, optionally substituted by 1 to 3 R7 groups; and
R7 represents:
a halogen atom;
an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms;
a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical having 3 to 6 carbon atoms;
a nitro or cyano group;
an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms; or
a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted;
and the corresponding agriculturally acceptable salts.
Certain specific compounds of the formula (I), having the formula (Ia): 
wherein W, R1 to R6 and n have the same meaning as in formula (I), are known. Denoted S-alkylated derivatives of 5,5diphenyl-2-thiohydantoin and of 5,5-diphenyldithiohydrantoin, those particular compounds have been especially studied for their pharmacological properties, as described in:
(a) Zejc, A., Dissertations Pharmaceuricae er pharmacologicae, Warsaw, 20 (5), 507-524 and 525-537 (1968);
(b) Lucka-Sobstel, B. and Zejc, A., Dissertationes Pharmaceuticae er pharmacologicae, 22 (1), 13-19 (1970); and
(c) Fetter, J., Harsanyi, K, Nyitrai, J. and Lempert, K., Acta Chemica (Budapest), 78 (3), 325-333 (1973).
No agricultural fungicidal activity has been previously described for these compounds.
Other specific compounds of formula (I) have been described by (d) Bohme, Martin and Strahl in Archiv der Pharmazie, 313, 10-15 (1980). They are the three compounds of the formula: 
wherein R is H, CH3 or phenyl. These compounds are thus included in the compounds of formula (Ib), which form part of the invention: 
wherein W and R1 to R5 have the same meaning as in formula (I) above.
In this first major aspect of the invention, the compounds which are preferred for their better fungicidal activity and/or their ease of synthesis are:
(1) the compounds of formula (Ib);
(2) the compounds of formula (I), in particular those of formula (Ib), in which R5 is a hydrogen atom;
(3) the compounds in which R1 and R2 are different from H;
(4) the compounds in which R2 represents an alkyl group having 1 to 3 carbon atoms;
(5) the compounds in which R1 represents a phenyl ring, optionally substituted by R7;
(6) the compounds in which R3 represents an alkyl group having 1 to 3 carbon atoms;
(7) the compounds in which R4 represents a phenyl ring, optionally substituted by R7; and
(8) the compounds in which R3 represents a methyl group.
In a second major aspect of the present invention, the objects of the invention noted hereinabove can be achieved by virtue of compounds of the invention which are 2-imidazoline-5-one and 2-imidazoline-5-thione derivatives of the general formula (Ixe2x80x2): 
wherein:
W is a sulfur or oxygen atom or an Sxe2x95x90O group, as defined with formula (I) hereinabove;
n=0 or 1, as defined with formula (I) hereinabove;
Axe2x80x2 represents NR5 or O or S or CR5R6 or SO2 or Cxe2x95x90O;
R1 and R2, which are identical or different, and which are as defined with formula (I) above, represent:
H, provided that one of the two groups is different from H;
an alkyl or haloalkyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical having 2 to 6 carbon atoms;
a diallaminoalkyl or cycloalkyl radical having 3 to 7 carbon atoms;
an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7; or
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above in connection with formula (Ixe2x80x2);
or R1 and R2 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R7;
R30 represents:
a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms;
a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkycarbamoylalkyl group having 3 to 6 carbon atoms; or
an N,N-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms;
R40 represents:
a hydrogen atom (when n is equal to 1);
an alkyl group having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms;
a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms;
an N,N-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms;
an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7;
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above with respect to formula (Ixe2x80x2);
an amino group disubstituted by two identical or different groups chosen from:
an alkyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkenyl or alkynyl radical having 3 to 6 carbon atoms;
a cycloalkyl radical having 3 to 7 carbon atoms;
an arylalkyl, such as defined above with respect to formula (Ixe2x80x2), phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7; and
a thienylmethyl or furfuryl radical; or
a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl having 1 to 3 carbon atoms;
R5 is as defined with formula (I) above and represents:
H, except when R40 is H;
an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or cyanoalkylsulfonyl radical having 2 to 6 carbon atoms;
an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical having 3 to 6 carbon atoms;
a formyl radical;
a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical having 3 to 6 carbon atoms;
a cycloalkylcarbonyl radical having 4 to 8 carbon atoms;
a phenyl; arylalkylcarbonyl, especially phenylacetyl or phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups chosen from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups chosen from R7; (alkylthio)carbonyl; (haloakylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)carbonyl; (pyridylmethylthio)carbonyl; or arylsulfonyl radical; or
a carbamoyl radical, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R7 groups;
a sulfamoyl group, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R7 groups; or
an alkylthioalkylsulfonyl group having 3 to 8 carbon atoms or a cycloalkylsulfonyl group having 3 to 7 carbon atoms;
R6 is as defined with formula (I) above and represents:
a hydrogen atom;
a cyano group;
an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms;
an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms; or
a benzoyl group, optionally substituted by 1 to 3 R7 groups; and
R7 is as defined with formula (I) above and represents:
a halogen atom;
an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms;
a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical having 3 to 6 carbon atoms;
a nitro or cyano group;
an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms; or
a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted;
and the corresponding agriculturally acceptable salts and the optically active isomers;
with the proviso that when n=0, R40 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid.
Certain compounds belonging to the family of the 2-imidazolin-5-ones of general formulae: 
are known for their herbicidal properties from the documents of European Patents 41623, 41624, 215,738, 226947, 261705, 303863, 433655 and 436483 and U.S. Pat. No. 4,925,944, DE 3913757, GB 2167062, GB 2192877 and JP 3196570.
The imidazolinones of the formulae: 
have been described for their pharmaceutical properties by published applications WO 9114679, JP 8055467 and DE 1176660 and 1258412, respectively. No agricultural fungicidal activity has been described for compounds of formula (Ixe2x80x2).
The compounds of formula (Ixe2x80x2a): 
wherein R1, R2, R30, R40, R5 and W are as defined with formula (Ixe2x80x2) are novel.
In this second major aspect of the invention, the compounds which are preferred for their better fungicidal activity and/or for their ease of synthesis are:
(1) the compounds of formula (Ixe2x80x2a);
(2) the compounds of formula (Ixe2x80x2), in particular those of formula (Ixe2x80x2a), in which R5 is a hydrogen atom;
(3) the compounds in which R1 and R2 are other than H;
(4) the compounds in which R2 represents an alkyl group having 1 to 3 carbon atoms, preferably methyl;
(5) the compounds in which R1 represents the phenyl ring, optionally substituted by R7;
(6) the compounds in which R30 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, optionally substituted by one or more halogens, methoxy or methylthio;
(7) the compounds in which R40 represents the phenyl ring, optionally substituted by R7; and
(8) the compounds of formula (Ixe2x80x2) in which W represents an oxygen atom.
In a third major aspect of the present invention, the objects of the invention noted hereinabove can be achieved in whole or in part as a result of compounds of the invention which are derivatives of 2-alkoxy-2-imidazolin-5-ones of the general formula (Ixe2x80x3): 
wherein:
R11 represents an aryl or heteroaryl radical having 1 or 2 rings and from 5 to 10 ring atoms, from 0 to 3 of the ring atoms being heteroatoms, which can be the same or different, selected from the group consisting of N, O and S, at least one ring being aromatic or heteroaromatic, said aryl or heteroaryl radical being optionally substituted by from 1 to 3 R61 groups, which can be the same or different (R11 preferably being phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, each of these radicals being optionally substituted by from 1 to 3 groups selected from among the meanings of R61);
R21 represents an alkyl or haloalkyl radical having from 1 to 3 carbon atoms, the haloalkyl radical having 1 or more halogen atoms as substituents;
or R11 and R21 form, together with the ring carbon atom to which they are bonded, a carbocyclic or heterocyclic ring having from 5 to 7 atoms and from 0 to 3 hetero ring atoms, which can be the same or different, selected from the group consisting of N, O and S, said ring being optionally fused to a benzene ring, the ring system being optionally substituted by from 1 to 3 R61 groups, which can be the same or different;
R31 represents an alkyl or haloalkyl radical having from 1 to 3 carbon atoms, the haloalkyl radical being substituted by 1 or more halogen atoms;
R41 represents an aryl or heteroaryl radical having 1 or 2 rings and from 5 to 10 ring atoms, from 0 to 3 of the ring atoms being heteroatoms, which can be the same or different, selected from the group consisting of N, O and S, at least one ring being aromatic or heteroaromatic, said aryl or heteroaryl radical being optionally substituted by from 1 to 3 R61 groups, which can be the same or different (R41 preferably being phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, each of these radicals being optionally substituted by from 1 to 3 groups selected from among the meanings of R61);
R51 represents hydrogen, formyl, acyl having from 2 to 6 carbon atoms, aroyl, alkoxycarbonyl having from 2 to 6 carbon atoms, aryloxycarbonyl, alkylsulfonyl having from 1 to 6 carbon atoms or arylsulfonyl, the aryl portion of the aroyl, aryloxycarbonyl and arylsulfonyl radicals having from 6 to 10 carbon atoms and being optionally substituted by from 1 to 3 R61 groups, which can be the same or different; and
R61 represents:
a halogen atom;
an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio or alkylsulfonyl radical having from 1 to 6 carbon atoms, the haloalkyl, haloalkoxy and haloalkylthio radicals bearing 1 or more halogen atoms as substituents;
a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical having from 3 to 6 carbon atoms, the halocycloalkyl radical bearing 1 or more halogen atoms as substituents;
a nitro, cyano or thiocyanato group;
an amino radical optionally mono- or disubstituted by an alkyl or acyl radical having from 1 to 6 carbon atoms or an alkoxycarbonyl radical having from 2 to 6 carbon atoms; or
a phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radical, each of which can be optionally substituted by one or more of the following groups:
a halogen atom;
an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having from 1 to 6 carbon atoms, the haloalkyl, haloalkoxy and haloalkylthio radicals bearing 1 or more halogen atoms as substituents;
a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical having from 3 to 6 carbon atoms, the halocycloalkyl radical bearing 1 or more halogen atoms as substituents;
a nitro, cyano or thiocyanato group;
an amino radical optionally mono- or disubstituted by an alkyl or acyl radical having from 1 to 6 carbon atoms or an alkoxycarbonyl radical having from 2 to 6 carbon atoms; or
a phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radical;
and the corresponding agriculturally acceptable salts.
Preferred compounds of this third major aspect of the invention have the formula: 
wherein R21 to R61 have the same meanings as above and nxe2x80x3 is 0, 1, 2 or 3.
R41 preferably represents phenyl, substituted phenyl, pyridyl or substituted pyridyl. R51 preferably represents hydrogen or acyl (e.g. acetyl).
In a fourth major aspect of the present invention, it has been found that the objects of the invention noted hereinabove can be accomplished by means of fungicidal optically active 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives. The corresponding racemic compounds are compounds of formulae (I), (Ixe2x80x2) and (IIxe2x80x3) hereinabove, which are described in earlier copending parent U.S. Ser. No. 07/993,700 filed Dec. 21, 1992 (corresponding to European Patent Publication No. EP 0551048, published Jul. 14, 1993), in earlier copending parent U.S. Ser. No. 08/156,647, filed Nov. 24, 1993 (corresponding to European Patent Publication No. EP 0599749, published Jun. 1, 1994), and in earlier copending parent International Application No. PCT/FR93/00647, filed Jun. 29, 1993 (published as International PCT Publication No. WO 94/01410, on Jan. 20, 1994); optically active isomers are described in earlier copending parent International Application No. PCT/FR93/00647 and most especially in earlier copending parent U.S. Ser. No. 08/262,459, filed Jun. 20, 1994.
In accord with the fourth major aspect of the present invention, it has been discovered that one of the optical isomers of the racemic compounds referred to above has a biological activity which is much greater than that of the other isomer and that of the racemic mixture.
A further object of the present invention is therefore to provide new optically active compounds which are useful in controlling fungal diseases of crops.
Another further object of the invention is to provide new 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives which are active at a dose which is reduced with respect to that of the racemic derivatives.
It has been found that these objects can be achieved by virtue of the products of the invention which are optically active 2-imidazolin-5-one or 2-imidazoline-5-thione derivatives of general formula (Ixe2x80x2xe2x80x3): 
wherein:
W represents an oxygen or sulfur atom or an Sxe2x95x90O group;
M represents an oxygen or sulfur atom, or an optionally halogenated CH2 radical;
p is an integer equal to 0 or 1;
* means the asymmetric carton atom corresponding to a stereospecific configuration;
R12 and R22 are different and represent:
an alkyl or haloalkyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical having 2 to 6 carbon atoms;
a dialkylaminoalkyl or cycloalkyl radical having 3 to 7 carbon atoms;
an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R62; or
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above with respect to formula (Ixe2x80x2xe2x80x3);
or R12 and R22 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R62;
R32 represents:
a hydrogen or an optionally halogenated C1-C2 alkyl radical, when p is equal to 0 or (M)p is a CH2 radical; or
an optionally halogenated C1-C2 alkyl radical, when (M)p represents an oxygen or sulfur atom;
R42 represents:
the hydrogen atom;
an alkyl group having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms;
a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms;
an N,N-dialkycarbamoylalkyl group having 4 to 8 carbon atoms;
an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R62; or
an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above with respect to formula (Ixe2x80x2xe2x80x3);
R52 represents:
H, except when R42 is H;
an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl radical having 1 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or cycloalkylsulfonyl radical having 2 to 6 carbon atoms;
an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical having 3 to 6 carbon atoms;
the formyl radical;
a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical having 3 to 6 carbon atoms;
a cycloalkylcarbonyl radical having 4 to 8 carbon atoms;
a phenyl; arylalkylcarbonyl, especially phenylacetyl or phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups chosen from R62; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups chosen from R62; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)carbonyl; (pyridylmethylthio)carbonyl or arylsulfonyl radical;
a carbamoyl radical, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R62 groups;
a sulfamoyl group, optionally mono- or disubstituted by:
an alkyl or haloalkyl group having 1 to 6 carbon atoms;
a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms;
an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms; or
a phenyl, optionally substituted by 1 to 3 R62 groups; or
an alkylthioalkylsulfonyl group having 3 to 8 carbon atoms or a cycloalkylsulfonyl group having 3 to 7 carbon atoms;
or R42 and R52, taken together, can form, with the nitrogen atom to which they are attached, a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by an alkyl having 1 to 3 carbon atoms;
R62 represents:
a halogen atom;
an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms;
a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical having 3 to 6 carbon atoms;
the nitro or cyano group;
an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms; or
a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted by 1 to 3 groups, which are identical or different, chosen from R72; and
R72 represents:
a halogen atom chosen from fluorine, chlorine, bromine or iodine;
a linear or branched alkyl radical having from 1 to 6 carbon atoms;
a linear or branched alkoxy or alkylthio radical having from 1 to 6 carbon atoms; or
a linear or branched haloalkoxy or haloalkylthio radical having from 1 to 6 carbon atoms;
a nitrile radical; or
a nitro radical.
The invention also relates to the agriculturally acceptable salified forms of the compounds of formula (Ixe2x80x2xe2x80x3).
According to a preferred variant of the fourth major aspect of the invention, the optically active compounds according to the invention have the formula (Ixe2x80x2xe2x80x3a): 
in which the various symbols have the same meaning as in the formula (Ixe2x80x2xe2x80x3).
Finally, the compounds of the fourth major aspect of the invention will advantageously be chosen from the compounds of formula (Ixe2x80x2xe2x80x3a) in which W represents an oxygen atom.
In accord with the present invention, it has been found that the configuration of the asymmetric carbon atom marked with an asterisk (*) in formula (Ixe2x80x2xe2x80x3), i.e. in the 4-position of the ring, is very important to the fungicidal activity of the compounds of formula (Ixe2x80x2xe2x80x3) and that one of the two optical isomers, or enantiomers, has much greater fungicidal activity than the other member of the pair. It is therefore especially desirable to produce the enantiomer which has the greater fungicidal activity of the pair in optically pure form or to produce optically active compound in a form which is greatly enriched in the more fungicidally active enantiomer, for use in fungicidal compositions and for treating or preventing fungal disease. By xe2x80x9cgreatly enrichedxe2x80x9d form, it is meant that the optically active compound of formula (Ixe2x80x2xe2x80x3) contains no more than 20%, preferably no more than 5%, of the less fungicidally active of the pair of enantiomers. In other words, when the optically active compound of formula (Ixe2x80x2xe2x80x3) is in greatly enriched form, it should contain at least 80%., preferably at least 95%, of the more fungicidally active of the pair of enantiomers.
The compounds of formula (Ia) can be prepared according to the processes known per se described in the references (a) through (c) mentioned hereinabove in regard to formula (Ia) and in one of the following references:
(e) Biltz, H., Chemische Berichte, 42, 1792-1801 (1909);
(f) Chattelain, M. and Cabrier, P., Bulletin de la Socixc3xa9txc3xa9 Chimique de France, 14 (1947), 639-642;
(g) Carrington, C. H. and Warring, W. S., Journal of the Chemical Society, (1950), 354-365;
(h) Lampert, K., Breuer, J. and Lemper-Streter, M., Chemische Berichte, 92, 235-239 (1959);
(i) Shalaby, A. and Daboun, H. A., Journal fxc3xcr Praktische Chemie, 313 (6), 1031-1038 (1971);
(j) Simig, G., Lemper, K. and Tamas, J., Tetrahedron, 29 (22), 3571-3578 (1973);
(k) Schmidt, U., Heimgartner, H. and Schmidt, H., Helvetica Chemica Acta, 62 (1979), 160-170; or
(l) Muraoka, M., Journal of the Chemical Society, Perkin Transactions I, (1990), 3003-3007;
or according to one of the processes A, B, C or D described below.
The compounds of formula (Ib) can be obtained according to the process described by Bxc3x6hme, Martin and Strahl in Archiv der Pharmazie, 313, 10-15 (1980) [reference (d) hereinabove] or according to one of the processes described below.
Process A: Process for the Preparation of the Compounds of Formula (I)
The preparation of the compounds of formula (I) in which A is S by S-alkylation of the 2-thiohydantoins of formula (a) below is carried out according to the reaction scheme: 
wherein R1, R2, R3, R4, B, W and a are as defined with formula (I) hereinabove and wherein X represents a chlorine, bromine or iodine atom or a sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group, alkyl and aryl being as defined above for R1 and R2. It is possible to use, as base, an alkoxide, for example potassium tert-butoxide, an alkali metal or alkaline-earth metal hydroxide, an alkali metal carbonate or a tertiary amine. It is possible to use, as solvent, ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols having 1 to 3 carbon atoms, or aromatic solvents, for example tetrahydrofuran, at a temperature of between xe2x88x925xc2x0 C. and +80xc2x0 C.
This process is suitable for the compounds in which W represents a sulfur or oxygen atom.
The 2-thiohydantoins of formula (II) above can be obtained according to processes described in the literature such as, for example, in the following references:
(e) Biltz, H., Chemische Berichte, 42, 1792-1801 (1909);
(n) Eberly and Dains, Journal of the American Chemical Society, 58, (1936), 2544-2547;
(o) Carrington, C. H., Journal of the Chemical Society, (1947), 681-686;
(g) Carrington, C. H. and Warring, W. S., Journal of the Chemical Society, (1950), 354-365;
(h) Lampert, K., Breuer, J. and Lemper-Streter, M., Chemische Berichte, 92, 235-239 (1959); or
(i) Koltai, E., Nyitrai, I., Lempert, K. and Burics, L., Chemische Berichte, 104, 290-300 (1971);
or alternatively according to one of processes E or F described below and which form part of the invention.
Process B: Process for the Preparation of the Compounds of Formula (Ic)
The preparation of the 2-methylthio-2-imidazolin-5-ones of formula (Ic) below by cyclization of the iminodithiocarbonates of formula (V) below is carried out according to the overall scheme: 
wherein R1, R2, R4, B and a are defined as with formula (I) above.
Step (a):
The iminodithiocarbonates (I) can be prepared by carrying out the preparation according to the conditions described in the literature for analogous compounds, for example C. Alvarez Ibarra et at, Tetrahedron Letters, 26 (2), 243-246 (1985) or E. Melendez et al, Synthesis, 1981, 961, according to the scheme: 
Step (b):
The compounds of formula (V) are obtained by condensing the compounds of formula (III) with amines or hydrazines of formula (IV). To carry out the condensation, the acid (III) must be activated in the acid chloride form, in the dicyclohexylisourea form using dicyclohexylcarbodiimide or in the imidazolide form using carbonyfdimidazole. Condensation is carried out under the usual conditions for this type of reaction.
Step (c):
Cyclization of the compounds (V) is carried out by simple heating in an aromatic solvent at reflux. It is possible to use, as solvent, especially xylene, chlorobenzene or dichlorobenzene.
Process C: Derivatization of the Compounds of Formulae (Ibb) and (Idd)
Process C1: Process for the Preparation of the Compounds of Formula (Ib) By N-derivatization of the Compounds of Formula (Ibb)
The compounds of formula (Ibb), that is, the compounds of formula (Ib) in which R5 is a hydrogen atom, can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated according to the following general scheme: 
wherein R5 is other than H, i.e. wherein R5 represents an alkyl, alkoxycarbonyl acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group, such as defined above with respect to formula (I); X represents a halogen, a sulfate group or an optionally substituted phenoxy, or an alkylsulfonyloxy or arylsulfonyloxy group, or a group R5xe2x80x94O, when R5 is acyl; and the other structural variables are defined as before with formula (I).
It is possible to use, as base, alkali metal hydrides, alkoxides or a tertiary amine. The reaction can be carried out at a temperature of between xe2x88x9230xc2x0 C. and +50xc2x0 C. It is possible to use as solvent, for example, ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide or aromatic solvents.
Carbamoylation of the compounds (Ibb) can be carried our by reacting them with isocyanates or isothiocyanates according to the scheme: 
The reaction is carried out under the same conditions as those described above, it being possible for the base, however, to be used in catalytic quantity.
Process C2: Process for the Preparation of the Compounds of Formula (Id)
The compounds of formula (Idd), that is, the compounds of formula (Id) in which R2 is a hydrogen atom, can be alkylated in the deposition according to the scheme: 
wherein X represents a chlorine, bromine or iodine atom, and the other substituents are defined as before except that R2 is other than H, in an organic solvent in the presence of base. It is possible to use, as base, an alkoxide, a metal hydride or an amide. The reaction can be carried out at a temperature of between xe2x88x9230xc2x0 C. and +80xc2x0 C. It is possible to use, as solvent, ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide or aromatic solvents.
Process D: Process for the Preparation of S-oxidized Derivatives of the 2-imidazoline-5-thiones of Formula (I)
The compounds of formula (I) in which W represents a Sxe2x95x90O group are obtained by S-oxidizing the corresponding 2-imidazoline-5-thiones of formula (I) according to the scheme: 
wherein R1, R2, R3, R4, A, B and n are defined as before. It is possible to use peroxides, especially peracids, as the oxidizing agent. The oxidizing agent must be used in a stoichiometric quantity. Oxidation is carried out in chloroform or in methylene chloride at a temperature of between xe2x88x9220xc2x0 C. and +20xc2x0 C.
Process E: Preparation of the Dithiohydantoins of Formula (VI) Below
The dithiohydantoins of formula (VI) below can be obtained by trapping the alpha anions of the isothiocyanates with isothiocyanates which cannot form anions according to the scheme: 
wherein R1, R2 and R4 are defined as with formula (I), provided that at least one of the groups R1 or R2 must be electron-withdrawing (aryl, substituted aryl, alkoxycarbonyl, or the like). The isothiocyanate R4xe2x80x94NCS must not be able to form an anion; aryl isothiocyanates can be used in particular in this reaction. The reaction is carried out in the presence of base. It is possible to use, as base, potassium tert-butoxide, lithium or sodium bis(trimethylsilyl)amide or alkali metal hydrides. It is possible to use ethers or cyclic ethers as solvent. The reaction is carried out at a temperature below xe2x88x9260xc2x0 C. The anion must be trapped as it is formed. To achieve this, the mixture of the two isothiocyanates is run onto the base in solution at a temperature below xe2x88x9260xc2x0 C.
Process F: Preparation of the 2-thiohydantoins of Formula (VII) Below
The preparation of the 2-thiohydantoins (VII) from the isothiocyanates derived from the amino acids (VIII) is carried out according to the reaction: 
wherein R1, R2, R4, B and n Save the same meanings as with formula (I).
Cyclizaton can be carried out in two ways:
thermally: in this case, the mixture of the reactants is heated at a temperature of between 110xc2x0 C. and 180xc2x0 C. in an aromatic solvent, such as toluene, xylene or the chlorobenzenes;
in basic medium: the cyclization is carried out in the presence of one equivalent of a base, such as an alkali metal alkoxide, an alkali metal hydroxide or a tertiary amine. Under these conditions, cyclization takes place at a temperature of between xe2x88x9210xc2x0 C. and +80xc2x0 C. It is possible to use ethers, cyclic ethers, alcohols, esters, DMF, DMSO and the like as solvent. The mixture is subsequently neutralized at room temperature.
The isothiocyanates can be prepared according to one of the processes mentioned in Sulfur Reports, 8 (5), 327-375 (1989).
Process G: Preparation of the Compounds of Formula (I) in a Single Stage
During cyclization of the 2-thiohydantoins according to process F, if the cyclization is carried out in basic medium, the thiohydantoin is in the thiolate form at the end of the reaction and can be reacted directly with an alkyl halide (chloride, bromide or iodide) or all sulfate R3X or with R3X in which X is an alkylsulfonyloxy or arylfonyloxy to form the corresponding compound of formula (I). Processes A and F are thus linked together according to the scheme: 
Process H: Preparation of the Compounds of Formula (Ie), that is the Compounds of Formula (I) in which (B)n is a Sulfur Atom
These compounds can be obtained by reacting a sulfuryl chloride R4SCl with an imidazolinone of formula (IX) according to the scheme: 
wherein R1, R2, R3 and R4 are as defined with formula (I).
The reaction is carried out at a temperature of between xe2x88x9220xc2x0 C. and +30xc2x0 C., in the presence of one molar equivalent of a base. As base, it is possible to use alkali metal hydrides, alkali metal alkoxides or tertiary amines. As solvent, it is possible to use polar solvents, for example ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide or aromatic solvents. The imidazolinones of formula (IX) can be prepared by processes analogous to process A above.
Process A
Compounds of formula (Ixe2x80x2) in which n=0, that is, compounds having the formula (Ixe2x80x2b): 
wherein the structural variables are as defined with formula (Ixe2x80x2) hereinabove, can be prepared according to standard processes described in the literature:
(1) Cyclization of an xcex1-amino acid amide of the formula: 
with a carboxylic acid orthoester of the formula:
R30xe2x80x94C(ORxe2x80x2)3
wherein Rxe2x80x2 represents a linear or branched alkyl radical having 1 to 4 carbon atoms, affords the corresponding compound of formula (Ixe2x80x2b). This process has been described, for example, by J. Brunken and G. Bach in Chem. Ber., 89, 1363-1373 (1956) and S. Ginsburg in J. Org. Chem, 27, 4062-4064 (1962).
The amino acid amides of the formula (X) above can be prepared conventionally by reacting an amine of formula R40NH2 with an amino acid ester of formula (XI): 
The reaction can then be carried out according to the conditions described by J. Brunken and G. Bach in Chem. Ber., 89, 1363-1373 (1956).
(2) Reaction of an amine R40NH2 with an iminoester of the formula (XII): 
affords the corresponding compound of formula (Ixe2x80x2b). This process has been described in J. Chem. Soc., 1959, 1648 by G. Shaw et al.
The iminoesters (XII) can be obtained by reaction of an amino acid ester (XI) with an imidate of the formula: 
as described in Ber. dt. Chem. Ges., 47, 2545 (1914).
(3) The compounds of formula (Ixe2x80x2c), that is, the compounds of formula (Ixe2x80x2b) in which R30 is a hydrogen atom, can be obtained by cyclization of an isonitrile derived from an amide of formula (XIII) in the presence of base, according to the scheme: 
This process has been described by Belgian Patent Application No. 862,194 of Dec. 22, 1977.
(4) The compounds of formula (Ixe2x80x2b) in which R2 is other than hydrogen can be obtained by alkylation of the corresponding compounds of the formula (Ixe2x80x2d), using a compound of the formula R2X as the alkylating agent, in basic medium according to the method described in the above-mentioned Belgian patent application, according to the scheme: 
wherein R2 is other than hydrogen
(5) Reaction of an amine of the formula R40NH2 with an azalactone of the formula (XIV): 
affords the corresponding compound of formula (Ixe2x80x2b). This reaction can be carried out by acid catalysis (acetic acid, for example) or by basic catalysis. An example of the latter case can be found in the article by Ito et al, Yakugaku Zasshi, 1975, 95(1), 28-32.
Process B
The compounds of formula (Ixe2x80x2a) can be obtained by analogy with one of the above-mentioned processes by reacting a hydrazine derivative of the formula R40NR5NH2 in place of the amine derivative of the formula R40NH2. They can also be prepared according to a process which forms part of the invention, by hot cyclization of a hydrazide of the formula (XV): 
The reaction is catalyzed by acids. Inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins or carboxylic acids can be used as the acid. The reaction can be carried out in aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, ester or alcohols. It is carried out at a temperature between 50xc2x0 C. and 150xc2x0 C. The reaction is generally carried out at the reflux temperature of the solvent, the water being distilled off as it is formed.
The hydrazides of formula (XV) can be prepared according to one of the processes described in the literature, for example as enumerated below:
(1) Reaction of certain hydrazines of the formula R40NR5NH2 with certain methyl, ethyl, propyl or butyl amino acid esters of the formula: 
as described by German Patent Application 1,089,390 of Sep. 22, 1960 (Chem. Ab., 1962, 56, 4860-4862), provides the corresponding hydrazides.
(2) Condensation of an N-acylated amino acid with a hydrazine in the presence of papain extracts in buffered aqueous solution according to the article by Niemann and Nichols in J. Biol. Chem., 143, 1942, 191-201, affords the corresponding hydrazide.
(3) Reaction of a hydrazine R40NR5NH2 with an azalactone of formula (XIV) hereinabove according to the reference by J. P. Branquet et al, Bull Soc. Chim. de France, 1965, (10), 2942-2954, affords the corresponding hydrazides.
The azalactones of formula (XIV) are themselves described in the above-mentioned article.
(4) A preferred general access route analogous to process B(2) above consists in activating the acid in the imidazolide form (Reaction a) or the mixed anhydride form (Reaction b) in order to condense it with a hydrazine, as depicted below:
Reaction a: 
Reaction b: 
The condensation is carried out under the usual conditions for this type of reaction, as is illustrated in Examples 12 and 13 hereinbelow.
Process C
Another preferred route for preparing the compounds of formula (Ixe2x80x2a) consists in reacting a hydrazine of the formula R40NR5NH2 with an azalactone of the formula (XIV) hereinabove under certain conditions:
(1) By heating the reactants in an inert solvent in the presence of an acid in order to catalyze the reaction. Halogenated hydrocarbons, esters, aromatic solvents or alcohols can be used as the solvent. Inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins or carboxylic acids can be used to catalyze the reaction. The reaction is carried out at a temperature from 50xc2x0 C. to 150xc2x0 C.
This process is illustrated in Example 15 hereinbelow.
(2) By heating the mixture of the reactants in acetic acid at reflux in the presence of sodium acetate in order to catalyze the reaction.
These conditions are illustrated in Example 16 hereinbelow.
Process D
The compounds of formula (Ixe2x80x2a) in which R5 is other than a hydrogen atom are also possible starting from compounds of the formula (Ixe2x80x2aa) below, which can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated by R5X in the presence of base and solvent: 
wherein R5 here represents an alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group, as defined above, and X represents a halogen, a sulfate or optionally substituted phenoxy group, or an alkylsulfonyloxy or arylsulfonyloxy group, or a group R5O, when R5 is acyl.
Alkali metal hydrides, alkoxides or a teriary amine can be used as base. The reaction can be carried out at a temperature between xe2x88x9230xc2x0 C. and +50xc2x0 C. Ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide or aromatic solvents, for example, can be used as solvent.
The carbamoylation or the thiocarbamoylation of the compounds of the formula (Ixe2x80x2aa) can be carried out by reaction with isocyanates or isothiocyanates according to the scheme: 
The reaction is carried out under the same conditions as those described above, it being possible, however, for the base to be used in a catalytic amount.
Process E
The compounds of formula (Ixe2x80x2ab) below, which are compounds of formula (Ixe2x80x2a) in which the group R30 is a hydrogen atom, can be obtained by reaction of dimethylformamide dimethyl acetal (DMFDMA) with an aminohydrazide of formula (XVI) according to the scheme: 
The reaction is carried out at a temperature between 10xc2x0 C. and 100xc2x0 C. in DMFDMA used in excess.
The intermediate aminohydrazides of formula (XVI) can be obtained according to a new process by reacting the hydrochloride of the acid chloride of the corresponding xcex1-amino acid in the presence of a base according to the scheme: 
The reaction is carried out at a temperature between xe2x88x9220xc2x0 C. and 40xc2x0 C. in cyclic or noncyclic ethers. Nitrogenous organic bases such as triethylamine or pyridine can be optionally used as the base. The intermediate acid chlorides can be obtained by the method described by S. Levine in J. Am. Chem. Soc., 1953, Volume 76, 1392. They are then obtained by reacting phosphorus pentachloride with the xcex1-amino acid according to the scheme below: 
The compounds of formula (Ixe2x80x3) are obtained by reacting 2-alkylthio-2-imidazolin-5-ones of formula (XVII) with an alcohol R31OH in the presence of strong base, according to the scheme: 
wherein R11, R21, R31 and R41 have the same meaning as in formula (Ixe2x80x3) hereinabove and R31 represents an alkyl group having from 1 to 3 carbon atoms.
As the strong base, an alkali metal alkoxide R31Oxe2x88x92M+, an alkali metal hydroxide or a strong organic base can be used. The reaction is preferably carried out in the alcohol R31OH as solvent, using the corresponding sodium alkoxide R31Oxe2x88x92Na+ as base. The reaction is carried out at a temperature of between about 20xc2x0 C. and 80xc2x0 C. The 2-alkylthio-2-imidazolin-5-ones of formula (XVII) are obtained according to one of the processes described hereinabove for the preparation of compounds of formula (I), in particular, for the preparation of compounds of formula (Ib) hereinabove. The acylation of the compounds of formula (Ixe2x80x3) in which R51 is a hydrogen atom, takes place according to classical methods.
Agriculturally acceptable salts of the compounds of formula (Ixe2x80x3) may be prepared by known methods.
The method of preparation of the compounds of formula (Ixe2x80x2xe2x80x3) is described in the following paragraphs, according to two process variants A and B. The symbols represented in formula (Ixe2x80x2xe2x80x3) and its intermediates which appear in this description of the method of preparation retain the same meaning as in the general definition of the compounds of formula (Ixe2x80x2xe2x80x3) hereinabove, unless another definition is expressly attributed to them.
Variant A
First Stage
A first stage of this variant consists of the preparation of the optical isomers of formula (Ixe2x80x2xe2x80x3) from xcex1-amino acids which are optically pure or greatly enriched in one enantiomer. Optically active compound greatly enriched in a specific enantiomer is understood to mean a compound containing at least 80%, preferably 95%, of this enantiomer.
The optical isomers of formula (Ixe2x80x2xe2x80x3) are prepared according to three series of processes, depending on the meaning of the (M)pxe2x80x94R32 group.
Process (1): Preparation of the compounds of formula (Ixe2x80x2xe2x80x3) in which p=1 and M=S and W=O:
The compounds of formula (Ixe2x80x2xe2x80x3) in which p=1 and M=S and W=O are prepared by reaction of the compound of formula (XVIII): 
wherein W represents an oxygen atom, with the compound of formula R32X, in which X represents the chlorine, bromine or iodine atom or the sulfate group or an alkylsulfonyloxy or arylsulfonyloxy group, alkyl and aryl being as defined above for R12 and R22. The reaction is carried out in a solvent and in the presence of a base. It is possible to use, as base, an alkoxide, for example potassium tert-butoxide, an alkali metal or alkaline-earth metal hydroxide, an alkali metal carbonate or a tertiary amine. It is possible to use, as solvent, ethers, cyclic ethers, all esters, acetonitrile, alcohols containing 1 to 3 carbon atoms or aromatic solvents, for example tetrahydrofuran, at a temperature between xe2x88x925xc2x0 C. and +80xc2x0 C.
A variant of the method described above consists in applying the so-called xe2x80x9cone-potxe2x80x9d process depicted below, which is described hereinabove for the preparation of compounds of formula (I). This method consists in starting directly from the isothiocyanate of formula (XIX) which is treated with a compound of formula (XX) in a solvent and in the presence of a base as described above. The intermediate of formula (XVIIIa) in the salt form is not isolated but is treated directly with the compound of formula R32X in which X has the same meaning as in the preceding paragraph. 
R is typically C1-C6 alkyl in formula (XIX) above.
The compound of formula (XVIII) in which W represents an oxygen atom can be prepared by a cyclization reaction between an isothiocyanate of formula (XIX): 
wherein R represents C1-C4 alkyl, and a compound of formula (XX): 
The cyclization reaction can be carried out in two ways:
(a) thermally in this case, the mixture of the reactants is heated at a temperature between 110xc2x0 C. and 180xc2x0 C. in an aromatic solvent such as toluene, xylene or chlorobenzenes;
(b) in the basic medium: the cyclization reaction is carried out in the presence of one equivalent of base such as an alkali metal alkoxide, an alkali metal hydroxide or a tertiary amine. Under these conditions, cyclization takes place at a temperature between xe2x88x9210xc2x0 C. and +80xc2x0 C. It is possible to use, as solvent, especially ethers, cyclic ethers, alcohols, esters, DMF or DMSO.
The isothiocyanates of formula (XIX) can be prepared according to one of the processes mentioned in Sulfur Reports, Volume 8 (5), 327-375 (1989), from the xcex1-amino acid of formula (XXI) via the amino ester of formula (XXII): 
in a way well known to those skilled in the art.
The amino esters of structure (XXII) can be obtained in a known way by:
(a) diastereoselective amination of a prochiral compound followed by deprotection of the chiral moiety as described by R. S. Atkinson et al, Tetrahedron, 1992, 48, 7713-30;
(b) resolution of the corresponding racemate with a chiral compound as described by Y. Sugi and S. Mitsui, Bull. Chem. Soc. Japan, 1969, 42, 2984-89; or
(c) esterification of a chiral amino acid as described by D. J. Cram et al, J. Am. Chem. Soc., 1961, 83, 2183-89.
Process (2): Preparation of the optical isomers of formula (Ixe2x80x2xe2x80x3) in which p=1 and M=O and W=O:
The compounds of formula (Ixe2x80x2xe2x80x3) in which p=1 and M=O and W=O are prepared by reacting the corresponding compound of formula (Ixe2x80x2xe2x80x3) in which p=1 and M=S [according to a process described hereinabove for the preparation of compounds of formula (I)] with an alcohol of the formula R32OH, in a solvent, in the presence of a strong base and at a temperature between 50xc2x0 C. and 80xc2x0 C. It is possible to use, as the strong base, an alkali metal alkoxide R32Oxe2x88x92Met+, in which Met+ represents an alkali metal or alkaline-earth metal, an alkali metal hydroxide or a strong organic base. The reaction is preferably carried out by selecting the alcohol R32OH as solvent and by using the corresponding sodium alkoxide R32Oxe2x88x92Na+ as base.
Process (3): Preparation of the optical isomers of formula (Ixe2x80x2xe2x80x3) in which p=0:
The compounds of formula (Ixe2x80x2xe2x80x3) in which p=0 and R32 is a hydrogen atom are obtained from the corresponding compound of formula (XXIII): 
by reacting the later with dimethylformamide dimethyl acetal (DMFDMA). The reaction is carried out at a temperate between 10xc2x0 C. and 100xc2x0 C., in excess DMFDMA.
The compound of formula (XXIII) is prepared from a compound of formula (XXIV): 
by reaction of the latter with the compound of formula (XX) above, at a temperature between xe2x88x9220xc2x0 C. and 40xc2x0 C., in a solvent consisting of a cyclic or non-cyclic ether, optionally in the presence of a base. The base is chosen from nitrogenous organic bases such as triethylamine or pyridine.
The compounds of formula (XXIV) can be obtained from the xcex1-amino acid of formula (XXI) by observing the method described by S. Levine in J. Am. Chem. Soc., 1953, Volume 76, 1392.
The optically active compounds of formula (Ixe2x80x2xe2x80x3) in which R32 is an optionally halogenated C1-C2 alkyl radical and in which p=0 or p=1 and M=CH2 are obtained from the compound of formula (XXV): 
in which R32 represents a C1-C3 alkyl radical, by reaction of the later with the compound of formula (XX) above, under conditions deduced, by analogy, from the method set out in the article by J. P. Banquet et al in Bull. Soc. Chem. de France, 1965, (10), 2942-2954.
The same article gives a procedure at the end of which the compound of formula (XXV) can be prepared from the xcex1-amino acid of formula (XXI).
Second Stare
The method of access to the optically pure or greatly enriched xcex1-amino acids of formula (XXI) used in the above stage is specified in this second stage of Variant A.
These xcex1-amino acids can be obtained according to one of the following methods:
(1) by diastereoselective synthesis and then suppression of the chiral moiety, as described by M. Chaari, A. Jenhi, J. P. Lavergne and P. Viallefont in Tetrahedron, 1991, 4, 4619-4630,
(2) by enzymatic resolution of the racemic amide, for which method the following references may usefully be consulted:
R. M. Kellog, E. M. Meijer et al, J. Org. Chem, 1988, 53, 1826-1828; and
D. Rossi and A. Calcagni, Experimentia, 1985, 41, 35-37;
(3) by hydrolysis of a chiral amino acid precursor such as, for example:
(a) a formyl amino acid of structure (XXVI) below, as described by MacKenzie and Clough, J. Chem. Soc., 1912, 390-397, or by D. J. Cram et al, J. Am. Chem. Soc., 1961, 83, 2183-89; or
(b) a hydantoin of structure (XXVII) as described in published British Patent Application No. 1,201,168: 
The compounds of formulae (XXVI) and (XXVII) can be obtained by resolution of the corresponding racemic modification with a chiral compound as described by MacKenzie and Clough, J. Chem. Soc., 1912, 390-397, or by D. J. Cram et al, J. Am. Chem Soc., 1961, 83, 2183-89, for the compound (XXVI); or as described in published International Patent Application No. 92/08702 for the compound (XXVII).
Variant B
According to a second variant of the process for the preparation of the optical isomers of formula (Ixe2x80x2xe2x80x3), the later are obtained from the corresponding racemic compounds by high performance liquid chromatography on a chiral stationary phase. A chiral stationary phase of Pirkle type with D-phenylglycine grafts is preferred.
The racemic compounds corresponding to the formula (Ixe2x80x2xe2x80x3) are prepared according to the methods described hereinabove for the preparation of the compounds of formulas (I), (Ixe2x80x2), and (Ixe2x80x3), which are the methods described and exemplified in parent U.S. Ser. No. 07/993,700, filed Dec. 21, 1992, parent U.S. Ser. No. 08/156,647, filed Nov. 24, 1993, and parent International Application No. PCT/FR93/00647, filed Jun. 29, 1993.
Another subject of the present invention is new optically active compounds useful especially as intermediates in the preparation of the compounds of formula (Ixe2x80x2xe2x80x3). These intermediates have the formulae (XVIII), (XIX), (XXI), (XXIII) and (XXII): 
wherein R12, R22, R42 and R52 have the s a me meanings as in the genera formula (Ixe2x80x2xe2x80x3) of the invention;
and the formula (XXV): 
wherein R12 and R22 have the same meaning as above and R32 represents an optionally halogenated C1-C3 all radical;
and the formula (XXVIIb): 
wherein R22 has the same meaning as above and R62 represents a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted by 1 to 3 groups, which are identical or different, chosen from R72 as defined above.